JPS6371857A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To enhance ozone resistance of a photosensitive body and to render it usable also as a positively electrifiable type by incorporating a specified spirobichroman compound in a photosensitive layer. CONSTITUTION:The photosensitive layer contains the spirobichroman compound represented by the formula shown on the right in which R1 is alkyl, alkenyl, alkoxy, aryl, or the like; each of R2 and R3 is H, halogen, alkyl, alkenyl, or the like; and R is alkyl, alkenyl, aryl, a heterocyclic group, or the like; R' is H, alkyl, alkenyl, R4CO-, or the like; and R4 is alkyl, alkenyl, or the like. This compound can be added to the photosensitive layer of a laminated structure or that of a single layer structure, thus permitting the obtained photosensitive body to the remarkably improved in potential drop due to corona discharge in the presence of ozone, and also used for the positively electrifiable type.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to electrophotographic photoreceptors, and more particularly to improvements in organic photoconductive electrophotographic photoreceptors.

[Prior art 1] In an electrophotographic copying machine using the Carlson method, after the surface of a photoreceptor is charged, an electrostatic latent image is formed by exposure, and the electrostatic latent image is developed with toner, and then the visible image is formed. Transfer and fix onto paper, etc. At the same time, the photoreceptor is subjected to removal of adhered toner, electrical gap, and surface cleaning, and is used repeatedly over a long period of time. Therefore, as an electrophotographic photoreceptor, it not only has electrophotographic properties such as good charging characteristics and sensitivity, and low dark decay, but also has good printing durability, abrasion resistance, moisture resistance, etc. after repeated use. Physical properties, ozone generated during corona discharge,
It is also required to have good resistance to ultraviolet rays and the like during exposure (environmental resistance). Conventionally, as electrophotographic photoreceptors, inorganic photoreceptors having a photosensitive layer mainly composed of an inorganic photoconductive substance such as selenium, zinc oxide, or cadmium sulfide have been widely used. On the other hand, the use of various organic photoconductive substances as materials for photosensitive layers of electrophotographic photoreceptors has been actively developed and researched in recent years. For example, in Japanese Patent Publication No. 50-10496, poly-N-
vinylcarbazole and 2.4,7. -) Rinitro 9-
An organic photoreceptor having a photosensitive layer containing fluorene/one is described. However, this photoreceptor is not necessarily satisfactory in sensitivity and durability. In order to improve these drawbacks, attempts have been made to develop organic photoreceptors with high sensitivity and durability by assigning charge generation R ability and charge transport function to different substances in the photosensitive layer. being done. This kind of FII
In the functional separation type electrophotographic photoreceptor, it is convenient to select substances that exhibit each function from a wide range of materials, so it is relatively easy to produce an electrophotographic photoreceptor with arbitrary characteristics. is possible. Many substances have been proposed as charge-generating substances that are effective for such functionally separated electrophotographic photoreceptors. Examples of using inorganic substances include, for example, Japanese Patent Publication No. 43-1619
As described in Publication No. 8, there is amorphous selenium. This is 8! Combined with a charge transport material. Furthermore, many electrophotographic photoreceptors using organic dyes or organic pigments as carrier-generating substances have been proposed. No. 22834, 54-
This is already known from publications such as No. 79632 and No. 56-116040. By the way, known photoreceptors using organic photoconductive substances are generally used for negative charging. The reason for this is that when negative charging is used, the mobility of holes among the charges is large, which is advantageous in terms of photosensitivity and the like. However, it has been found that using such negative charging causes the following problems. That is, the first problem is that ozone is likely to be generated in the atmosphere when negatively charged by the charger, worsening the environmental conditions. Another problem is that positive polarity toner is required for development of negatively charged photoreceptors, but does positive polarity toner cause friction against ferromagnetic charged particles? ! ? The problem is that it is difficult to manufacture from an electrical system perspective. Therefore, it has been proposed to use a photoreceptor using an organic photoconductive substance with positive charging.1 For example, a charge transport layer is laminated on a charge generation layer, and the charge transport layer is formed of a material with high electron transport ability. In the case of a positive charging photoreceptor, the charge transport layer contains trinitrofluorenone or the like, but this substance is unsuitable because it is carcinogenic. On the other hand, a photoreceptor for positive charging may be considered in which a charge generation layer is laminated on a charge transport layer with a large hole transport ability, but this has a very thin charge generation layer on the surface side, resulting in poor printing durability, etc. This is not a practical M configuration. In addition, as a photoreceptor for positive charging, U.S. Patent No. 361541
No. 4 Mei 111g1 contains a thiapyrylium salt (charge generating substance) so as to form a eutectic complex with polycarbonate (binder tree layer). However, this known photoreceptor has the drawbacks of a large memory phenomenon and a tendency to generate ghosts. US Patent No. 335
No. 7989 also discloses a photoreceptor containing 7-talosi-7ine, but the properties of 7-talosi-7ine change depending on the crystal form, and it is necessary to strictly control the crystal form. can be. Furthermore, the short wavelength sensitivity is insufficient and the memory phenomenon is large, making it unsuitable for copying machines that use light sources in the visible wavelength range. Due to the above-mentioned circumstances, conventionally, it has been difficult to use a positively charged photoreceptor made of an organic photoconductive substance, and for this reason, it has not been possible to elongate it with a negative charge of −1 μm. It was. OBJECT OF THE INVENTION The object of the present invention is to provide an organic photoconductive electrophotographic photoreceptor that can be used for positive charging, has good sensitivity, has excellent resistance to ozone, and is durable. Our goal is to provide the following.

[Configuration and effects of the invention]

The above object of the present invention is to provide a photosensitive layer of the following general formula [I] of an electrophotographic photoreceptor in which a photosensitive layer containing a charge generating substance and a charge transporting substance as main constituents is provided on a conductive support.
This was achieved by incorporating the compound shown in General formula (1) In the formula, R1 is an alkyl group, an alkenyl group, an aryl group,
represents an alkoxy group, an alk/oxy group, or an aryloxy group; %R2 and R1 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an alkoxy group; R is an alkyl group, an alkenyl group, a dichlorofurkyl group, a 7 aryl group, heterocyclic group, R, CO- group, R, 5o2-
group or R, NIICQ- group, Rt is a hydrogen atom,
Alkyl group, alkenyl group, R, CO- group, R, SO□
- group or R,NlIC0- group, R3 and V
R@ each represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R′ is R, CO
- group, R, SO□- group or R, N11C0- group, R and R' may be the same group or different groups. Ozone deterioration of the photoreceptor is caused by repeatedly applied corona discharge, but it is also thought to be enhanced by singlet oxygen generated by exposure. The degree to which ozone oxidation occurs varies depending on the composition of the photosensitive layer of the photoreceptor, the types of charge-generating substances and charge-transporting substances, etc., but charge-transporting substances are more susceptible to oxidation, especially organic photoconductive materials. When using sexual substances, the consequences are extremely large. As a result of intensive studies on improving ozone deterioration (particularly potential drop) of photoreceptors, the present inventors found that the general formula [I
The present inventors have discovered that a specific spirobiclone compound represented by the following formula not only effectively prevents ozone oxidation, but also contributes to improving other electrophotographic properties and physical properties. The present invention will be explained in more detail below. The compound used in the present invention is a compound obtained by substituting one or both of the 72/- hydroxyl groups of 6,6'-hydroxy-2,2'-subirobichroman. In the general formula (1) of the compound used in the present invention, examples of the alkyl group represented by R and 1' include methyl, ethyl, propyl, i-propyl, butyl, t
-butyl, i-pentyl, 5ec-pentyl, octyl, t-octyl, dodecyl, octadecyl, eicosyl, etc., alkenyl groups include allyl, octenyl, oleyl, etc., aryl groups include phenyl, naphthyl, etc. Examples of the alkoxy group include methoxy, ethoxy, butoxy, horse chestnut F+11.44
2615Mj7.1H 474:/-tklf+4(
Uj is a group such as allyloxy or hexenyloxy, and examples of the 7-aryloxy group include a phenyloxy group. Examples of the halogen atom represented by R2* or R5 include atoms such as fluorine, chlorine, and bromine; alkyl groups and alkenyl groups; and examples of the alkoxy group include the same groups as those described in R and 'c above. It will be done. Examples of the cycloalkyl group represented by R include groups such as cyclopentyl, cyclohexyl, and cyclooctyl; examples of the heterocyclic group include groups such as imidazolyl, furyl, thiazolyl, and pyridyl; examples of the alkyl group and alkenyl group include the above-mentioned R1 Examples include groups similar to those described in . The furkyl group and dialkenyl group represented by R' include the same groups as those described for R+. The alkyl group and aryl group represented by R, , R, or R6 are the same groups as described in R above, and the cycloalkyl group and heterocyclic group are the same groups as described in R above. Examples include groups. ! i! In addition, these alkyl groups, alkenyl groups, aryl groups
/10 dene atoms, alkyl groups, aryl groups, 7 alkoxy groups, 7 lyloxy groups, n/a groups, acyloxy groups, and alkoxycarbonyl groups. may be substituted with a substituent such as a group, an acyl group, a sulfamoyl group, a hydroxyl group, a nitro group, or an amide group. Further, the general formula (1) also includes a compound represented by the following general formula (n). General formula (n) In the general formula [■], R' t Rl , R2 and R3 have the same meanings as in the above general formula (1), and X is a substituted or unsubstituted fullkylene group, in the carbon chain of an alkylene group. 10-1-S-1-N^- (^: hydrogen atom, lower alkyl group, 7-enyl group, etc.), -5O2- or an alkylene group bonded via a phenylene group, -CO- X'
-CO-1-SO2-X'-5O2-* Taha-CO
NX-X'-NflCO-(X' is an alkylene group, 10-1-S-1-NΔ-(^:
hydrogen atom, lower alkyl group, phenylene group, etc.) or an alkylene group or phenylene group bonded via -SO,-. Furthermore, in the general formulas (1) and (I[), compounds in which R1 has a substituted or unsubstituted alkyl group, alkenyl group, or aryl group, and R2 and IR1 have a hydrogen atom or a substituted or unsubstituted furkyl group are useful. (ra substituent represents the above-mentioned substituent). Furthermore, in general formulas (1) and (Il), R1 is an alkyl group or a phenyl group which may be substituted with an alkyl group, R2 and R3 are a hydrogen atom, R is a 7-yonyl group (or an alkyl group, an alkenyl group, a cycloalkyl group, which may be substituted with an alkoxycarbonyl group, R, CO
group, R, SO□ group or R6 former ICO group, R2 and R@ are phenyl groups which may be substituted with furkyl groups or alkyl groups, and X is alkylene group or -CO-
Compounds having X'-CO- (X'' represents an alkylene group) are particularly useful. Typical specific examples of the compounds of the present invention are shown below. General formula (
Compounds of type n) These compounds are
6,6'-7hydroxy-4.4.4',4'-tetramethyl-2,2 obtained by the method described in No.-20977
It can be easily synthesized by alkylating or acylating a '-spirobichroman compound, and is disclosed in JP-A No. 5
It is also described in No. 3-20327. The amount of the compound represented by the above general formula used in the present invention (hereinafter referred to as the compound of the present invention) varies depending on the composition of the photoreceptor, the type of charge transport material, etc. 0.1~100mfl
L%, preferably 1 to 50% by weight, particularly preferably 5 to 50% by weight
It is used in a range of 1% by weight. Next, the structure of the photoreceptor of the present invention will be explained with reference to the drawings. The photoreceptor of the present invention is, for example, as shown in FIG.
A charge-generating N containing a charge-generating substance 5 (hereinafter sometimes referred to as CGH) and a binder resin as necessary is placed on a conductive support or sheet (several conductive layers).
J,2 (hereinafter sometimes referred to as CGL) is the lower layer,
Charge transport material 6 (hereinafter sometimes referred to as CTM) and charge transport layer 3 containing binder U (fat) as needed.
A photosensitive layer 4 having a laminated structure with a CTL (hereinafter sometimes referred to as CTL) as an upper layer, ti! As shown in Figure J2, a photosensitive layer 4 having a laminated structure with CTL3 as a lower layer and CCL2 as an upper layer is provided on a support 1, and as shown in Figure 3, CGL, CTM and necessary layers are provided on a support 1. Examples include those provided with a single-layer photosensitive layer 4 containing a binder resin depending on the requirements. In the same M configuration as shown in Fig. 2, both CGM and CTM may be contained in the upper CCL layer, and a protective layer (OCL) may be provided on the photosensitive layer. An intermediate layer may be provided in between, an example of which is shown in FIG. That is, the intermediate M7 is provided on the support 1, and the CT
CTL3 and CG containing N6a and binder resin
CC containing H5, C7M6b and binder resin
This photoreceptor has a photoreceptor layer 4 laminated with L2, and is further provided with a protective layer 8 containing a binder as a main component. The compounds of the present invention are CGL and CTL that constitute the photoreceptor. It may be contained in either a single-layer structure photosensitive layer or OCL, or it may be contained in multiple layers. The effects of the present invention are more clearly exhibited in a photoreceptor having a laminated structure in which CGL is an upper layer and CTL is a lower layer. Next, as the charge generating substance suitable for the present invention, both inorganic pigments and organic dyes can be used. S-shaped selenium, trigonal selenium, selenium-arsenic alloy, selenium-tellurium alloy, cadmium sulfide, cadmium selenide,
In addition to inorganic pigments such as cadmium selenide sulfide, mercury sulfide, lead oxide, and lead sulfide, organic pigments such as those shown in the following representative examples may also be used. (1) 7zo pigments such as monoazo pigments, polyazo pigments, metal complex azo pigments, pyrazolone azo pigments, stilbene azo and thiazole azo pigments. (2) Perylene pigments such as perylene anhydride and perylene imide. (3) anthraquinone derivatives, anthanthrone derivatives, nobenzbirenquinone derivatives, pyrantrone derivatives,
(4) Indigoid pigments such as indigo derivatives and thioindigo derivatives; (6) Indigoid pigments such as indigo derivatives and thioindigo derivatives (6); Carbonium j 1% pigments such as phenylmethane pigments, triphenylmethane pigments, xanthine pigments and 7-crinon pigments (7) Quinone imine IAR14 such as 7-gin pigments, oxanone pigments and thianone pigments (8) Methine pigments such as cyanine pigments and azomethine pigments Pigments (9) Quinoline pigments (10) Nitro pigments (11) Nitroso pigments (12) Benzoquinone and 17-toquinone pigments (13)
7-talimide pigments (14) Perinone-based pigments such as bisbenzimidazole derivatives Various 7-talimide pigments having electron-withdrawing groups are used because of their good electrophotographic properties such as sensitivity, memory phenomenon, and residual potential, but they have poor durability. Polycyclic quinone pigments are most preferred in terms of ozone properties. Although the details are unknown, it is probably because azo groups are susceptible to ozone oxidation (electrophotographic properties deteriorate, but polycyclic quinones are inert to ozone. Examples of the azo pigments that can be used include the following exemplified compound groups (1) to (V). (■ J: ,・-゛) Exemplary compound group CIII): ・′-\\\ Below is the margin ゞ・He-7・′ Exemplary compound [■]: Exemplary compound [■]: Also, the following poly-J11 quinones The example 1 virtual object group [■] to (1) consisting of the face τ1 can be most preferably used as CGM. : 115, Exemplary compound group [■]: Exemplary compound group [■]: Next, in the present invention, there are no particular restrictions on the acceptable charge transport substances, but for example, oxazole derivatives, oxadiazole derivatizations, thiazole derivatives. , triazole derivatives, triazole derivatives, imidazole derivatives, imidasilone derivatives, imidazolidine derivatives, bisimidazolidine derivatives, su-tyryl compounds, hydrazone compounds, pyrazoline derivatives, oxacilone derivatives, benzothiazole derivatives, Benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives, acridine derivatives, phenazine M!4 conductors, aminostilbene derivatives, poly-
N-vinylcarbazolene, poly-9-vinylanthracene, etc.) may be used. However, the support i114 of the hole that occurs during light illumination.
It is preferable to use a CTH that is suitable for combination with the carrier generated product τ in addition to having a high transport capacity □ to the above, and examples of such CTH include, for example, the following example 1 compound group (
IK ) or L) The still 1 hardware indicated by l is tt
Useful! Sign. Exemplary compound group (II): In addition, as CTM, the following exemplary compound groups [aims] to (XV)
A hydrazone compound represented by can also be used. Exemplary compound group [°C]: Exemplary compound I! ¥[,
) Exemplified Compound ↑1ffW¥ (XSI): In addition, amine derivatives shown in the following exemplified compound group [X■] can also be used as CT14. Exemplary compound group [X■]: The layer structure of the photosensitive layer of the photoreceptor of the present invention has a laminated structure and a single layer structure as described above.
L, single-layer photosensitive N or OCL, or multiple layers of 1 or 2 layers for the purpose of improving sensitivity, reducing residual potential or fatigue during repeated use, etc. Containing an electron-accepting substance of gi or more is deceptive. Electron-accepting substances that can be used in the photoreceptor of the present invention include:
For example, succinic anhydride, maleic anhydride, dibromaleic anhydride, 7-talic anhydride, tetrachlor 7-talic anhydride,
Tetrabromo-7thalic anhydride, 3-nitrophthalic anhydride,
4-nitro 7-talic anhydride, pyromellitic anhydride, mellitic anhydride, tetracyanoethylene, tetraschiftski 7-thalic anhydride, 0-dinitrobenzene, rice-dinitrobenzene, 1°3.5. -) +) Nitrobenzene, para-nitrobenzonitrile, vicryl chloride, chlorimito, chloranil, pullanil, 2-methylnatamine, nochlorobenzoquinone, anthraquinone, dinitroanthraquinone, trinitrofluorene,
9-fluorenyritene [dicyanomethylenemalononenitrile], polynitro-9-fluorenylidene [dicyanomethylenemalonodinitrile], picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3,5-nitrobenzoic acid [Examples include oral benzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-)nitrosalicylic acid, heptatalic acid, and the like. Examples of binder layers that can be used in the photosensitive layer in the present invention include polyethylene, polypropylene, acrylic resin, methacrylic resin, and vinyl chloride! Addition polymer resins, polyaddition resins, polycondensation resins such as resins, vinyl acetate resins, Ebotoshi resins, polyurethane resins, phenolic resins, polyester resins, Alkifdri resins, polycarbonate resins, silicone resins, melamine resins, and Copolymer resins containing two or more of the repeating units of these resins, such as vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-maleic anhydride copolymer resins, and other insulating resins. , poly-N-vinyl carbazole, etc. The intermediate layer may be an I1 adhesion layer or a barrier layer, etc.
The above binder U (in addition to fats, such as polyvinyl alcohol, ethyl cellulose, carpol dimethyl cellulose, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, casein, N-flucoxymethylated nylon, starch, etc. are used.Next, as the conductive support for supporting the photosensitive layer, metal plates, metal drums, or metal foils such as aluminum and nickel, aluminum, tin oxide, and indium oxide are used. A plastic film coated with a conductive material, a paper or plastic film coated with a conductive substance, or a drum can be used. 14 can be provided by a method of dissolving or dispersing it alone or with a suitable binder 1ffffff in a suitable solvent and applying it and drying it.When the above CCL is dispersed to form a CCL, the island CGL It is preferable that the particles have an average particle size of 2 μm or less, preferably 1 μm or less, that is, if the particle size is too large, dispersion in the layer will be poor, and some of the particles will protrude from the surface. The smoothness of the surface deteriorates, and in some cases, discharge may occur at the protruding parts of the particles, or the Y toner particles may adhere there, easily causing toner filming.However, if the particle size is too small, it may actually cause agglomeration. easy to do,
It is desirable to set the lower limit of the average grain size to 0.01 μ- because the resistance of the layer increases, the sensitivity and repeatability decrease due to an increase in crystal defects, and there is a limit to miniaturization of νt. . CGL can be provided by the following method. That is, the above-mentioned CGL is made into fine ta particles in a dispersion medium using a ball mill, a homomixer, etc., and a dispersion obtained by adding IZUINGU resin and stirring is applied. If the particles are dispersed under the action of ultrasonic waves in step -1 of this method, uniform dispersion is possible. N,N-trimethylformamide, benzene, toluene,
Examples include xylene, monochlorobenzene, 1,2-nochloroethane, nochloromethane, 1tl=2)lichloroethane, tetrahydro7rane, methyl ethyl ketone, ethyl acetate, and butyl acetate. Pine goo in CCL (11W 100 weight 1 part) C
GL is 20 to 200 parts by weight, preferably 25 to 100 parts by weight. If CGL is less than this, the photosensitivity will be low and the residual potential will increase, and if it is more than this, dark reduction will increase and the acceptance potential will decrease. The film thickness of the CGL formed as described above is preferably 1 to 10 μm in the case of a configuration for positive charging, and particularly preferably 3 to 7 μm in the case of a configuration for negative charging.
, OX to 10μ thick, particularly preferably 0.1 to 3μ thick. In other words, in the configuration for positive charging, CCL becomes the surface layer, so it lacks resistance to radiation, and in order to improve durability, it is necessary to increase the thickness of the CGL film, but this causes a decrease in sensitivity. However, this CTM (ICGH) has a structure that is more susceptible to biozone oxidation than ICGH, so if it is easily deteriorated by ozone, the durability of the photoreceptor will be impaired. CTL is obtained by dissolving and dispersing CTM described in a above in the same manner as CGL described above (i.e., dissolved and dispersed alone or together with the binder resin described above). It can be formed by coating and drying). CTl4 is 20 to 200 parts by weight, preferably 30 to 150 parts by weight, per 100 parts of binder resin in CTL. If the content of CTH is lower than this, light The sensitivity is poor and the residual potential tends to be high, and if the amount exceeds this amount, the solvent solubility deteriorates.The thickness of the CTM film to be formed is preferably 5 to 50 μl,
Particularly preferably 5 to 30 μl. Also, CGL and C
The film thickness ratio of TL is preferably 1:(1 to 30). In the case of the single barrel construction, the ratio of CGM contained in the binder resin is 20 parts per 100 parts by weight of the binder resin.
~200 parts by weight, preferably 25-100 parts by weight! It is considered to be Lg. If the content of CGH is less than this, the photosensitivity will be low and the residual potential will increase, and if it is more than this, the dark decay and acceptance potential will decrease. Next, the ratio of CTM to the binder resin is 20 to 200 m per part of binder resin @ 100 weight.
: Part 1, good*Li! 30-150! l! ff1fitlttle. If the content ratio of CTM is less than this, the photosensitivity will be poor and the residual potential will be high (prone), and if it is more than this, the solvent solubility will be poor (prone).
mf! It is preferable that the L ratio is 1:3 to 1:2. In the present invention, the protective layer provided as necessary has a volume resistivity of 101Ω·cm or more, preferably 1016Ω·ca+ or more, more preferably 101ff as a binder.
A transparent resin with a resistance of Ω/C or higher is used. In addition, the binder contains at least 50 parts by weight of a resin that is cured by light or heat.
% or more. Examples of such tJ4 resins that harden with light or heat include thermosetting acrylic resin layers, silicone resins, epoxy resins, urethane resins, urea resins, phenolic resins, polyester resins, alkyd resins, melamine resins, and photocurable resins.
There are cinnamon a resins and their copolymerized or cocondensed resins, as well as photo- or thermosetting resins used in electrophotographic materials!
All of the fat is used. Further, if necessary, less than 50% of a thermoplastic resin can be contained in the retention layer for the purpose of improving workability and physical properties (preventing cracks, imparting flexibility, etc.). Such thermoplastic AT resins include, for example, polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, butyral resin, polycarbonate resin, silicone resin, or a coproportion IIN thereof, such as vinyl chloride-acetic acid. Vinyl copolymer resins, vinyl chloride-vinyl acetate-maleic anhydride copolymer resins, polymeric organic semiconductors such as poly-N-vinylcarbazole, and other thermoplastic resins used in electrophotographic materials are all used. Further, the a-retaining layer contains an electron-accepting substance and has a L
/ II AJIJ? +Vmr14L n
rl'! +L19n#Eggplant may contain ultraviolet Ia@harvesting, etc. (dissolved in a solvent together with the binder,
For example, it is coated and dried by dip coating, spray coating, blade coating, roll coating, etc., and is formed to a layer thickness of 2 μm or less, preferably 1 μm or less. [Examples] The present invention will be explained below with reference to Examples, but the embodiments of the present invention are not limited thereby. Example 1 Vinyl chloride-vinyl acetate-
An intermediate layer having a thickness of 0.1 μl was formed from a maleic anhydride copolymer (S-LEC MF-10, manufactured by Tanezu Chemical Industry Co., Ltd.). Next, CTN (LY-75)/polycarbonate resin (
Panlite L-1250, Teijin Chemicals 91) = 75/
1 containing 16.511ff1% of 100 (weight ratio),
A 2-dichloroethane molten layer was dip coated onto the intermediate layer and dried to obtain a CTL having a thickness of 15 μm. Then sublimated as CGM 4, 10-knob mouth Moance 7thron (■-3)/Panlight L-1250 = 5
0/100 (weight ratio) was ground in a ball mill for 24 hours,
CTM (I!-7
5) to Panlite L-1250 at 75% by weight and the compound (12) of the present invention to CTH to 10fif
i% added. Monochlorobenzene was added to this dispersion to obtain monochlorobenzene/1,2-dichloroethane = 37
A CGL having a thickness of 5 μm was formed by spray coating on the CTL to obtain a photoreceptor of the present invention having a photosensitive layer having a laminated structure. Comparative Example I A comparative photoreceptor was obtained in the same manner as in Example 1 except that compound (12) in CCL was removed. Example 2 Compound (3) was substituted for compound (12) in Example 1.
) A photoreceptor of the present invention was obtained in the same manner as in Example 1 except for adding . Example 3 A photoreceptor obtained by removing compound (12) from the CCL of Example 1 (
thermosetting acrylic-melamine-epoxy (1:1:1) on the same photoreceptor of Comparative Example 1)! Monochlorobenzene/1,1.2-)dichloroethane (17
1 volume ratio) The coating solution obtained by dissolving in the mixed bath W100mUWS was spray applied and dried to form a 1μx thick RPI.
J was formed to obtain a photoreceptor of the present invention. Example 4 On the photoconductor obtained by removing compound (12) from the CGL of Example 1, a 0.1 μl thickness of Brimer PH91 for silicone hard coat (manufactured by Toshiba Silicon Co., Ltd.) was spray-coated, and then silicone hard coat was applied on top of the photoreceptor. Foot Toss Guard 51o (Toshiba Silicon Co., Ltd. 91) and compound (12) were added to resin 100.
tl! A solution added in an amount of 10 parts to 11 parts was spray applied and dried to form a protective layer with a thickness of 1 μm to obtain a photoreceptor of the present invention. Example 5 An intermediate layer exactly the same as in Example 1 was formed on a conductive support made of a polyester film laminated with an aluminum whistle. Next, as a coating liquid for CTL, 8% by weight of butyral resin (Elex BX-1, manufactured by Tanesui Kagaku Co., Ltd.) and CTH (r
A solution obtained by dissolving 6% by weight of X-75) in methyl ethyl ketone was applied onto the intermediate layer and dried to form a 10 μl thick CTL. Next, apply CGM (■-7) 0.2y to Paint Conditioner 1 (Paint Conditioner + Red).
Devi1 company! Grind for 30 minutes, then add Polycarbonate N! fJJlt (Panlight L-1250, Maebata)
After adding 8.3 g of a solution prepared by dissolving 0.5% by weight in a mixed solvent of 1,2-dichloroethane/1,1.2-)dichloroethane and dispersing for 3 minutes, polycarbonate resin, CTMCII-75 ) and compound (12
) wo, + j'L ('j'L3.3 times j1%, 2.
8mj15'6o, ): V 0°26 19.1g of a solution obtained by dissolving in a mixed solvent of 1,2-dichloroethane/1,1,2-trichloroethane to give a concentration of 1% by weight was added and further dispersed for 300 minutes. . The thus obtained dispersion was spray-coated onto the CTL and dried to form a CGL with a thickness of 5 μl, thereby obtaining a photoreceptor according to the present invention having a photosensitive layer having a laminated structure. Comparative Example 2 A comparative photoreceptor was obtained in the same manner as in Example 5 except that compound (12) in CCL was removed. Example 6 Compound (3) was substituted for compound (12) in Example 5.
) A photoreceptor of the present invention was obtained in the same manner as in Example 5, except that . Example 7 A photoreceptor obtained by removing the compound (12) from CGL of Example 5 (
A photoreceptor containing the compound (12) used in Example 3 was placed on the photoreceptor (same as the photoreceptor of Comparative Example 2). Il/W was provided to obtain a photoreceptor of the present invention. Example 8 A protective layer containing the compound (12) used in Example 4 was provided on a photoreceptor obtained by removing compound (12) from the CGL of Example 5 to obtain a photoreceptor of the present invention. Example 9 An intermediate layer similar to that of Example 1 was formed on a polyester film deposited with aluminum. Then, sublimed 4,10-nobromo7anthrone (
V! -3)40. in a porcelain ball mill with a 40rp wheel 2
Pulverized for 4 hours, 20g of Panlite L-1250 (mentioned above)
and 1300z1 of 1,2-dichloroethane were added, and further 2
The mixture was dispersed for 4 hours to obtain a CGL coating solution. This was applied on the intermediate layer to provide a CGL with a WX thickness of 1 μm. Next, 7.5 g of CTM (lX-61), Panlite L-
125010° and 0.75 g of compound (12) at 1,
The solution dissolved in 2-dichloroethane 80R2 was added to the CG
A photoreceptor of the present invention was prepared by coating the photoreceptor on L to form a CTL with a thickness of 15 μl. Comparative Example 3 A comparative photoreceptor was obtained in the same manner as in Example 9 except that compound (12) in the CTL was removed. Example 10 An intermediate layer exactly the same as in Example 1 was formed on a conductive support made of polyethylene terephthalate having a thickness of 100 μm and deposited with aluminum. Next, bisazo compound (■-7) 1,5.
to 1,2-dichloroethane/monoethanolamine (1
000/1 volume ratio) in a mixed solvent 100111 with a ball mill for 8 hours 1! A portion of the WX solution that had been heated to 1C was applied onto the above intermediate layer and sufficiently dried to form a CCL having a thickness of 0.3 μM. Then styryl compound (IX-43) 1 as CTM
A solution prepared by dissolving 1.25 g of Panlite L-1250 (above) and 1.1259 of compound (12) in 100 zi' of 1,2-dichloroethane was applied onto the CGL, and dried sufficiently to form a CTL with an IS μl thickness. A photoreceptor of the present invention was prepared. Comparative Example 4 A comparative photoreceptor was prepared in the same manner as in Example 10 except that compound (12) in the CTL was removed. The ozone resistance of the 14 types of photoreceptors thus obtained was evaluated in the following manner. That is, electrostatic test ff1 (
Roa for! ! Ozone generator (manufactured by Japan Ozone Co., Ltd., model 0-1-2) and ozone monitor (manufactured by Ebara Jitsugyo Co., Ltd., EC-2001)
Using an ozone fatigue tester equipped with a mold), the photoreceptor was tested at an ozone concentration of 90 ppm. The following characteristic tests were conducted. In other words, +6K for a positively charging photoreceptor.
V, in the case of a negative charging photoreceptor, apply a voltage of -6 KV and charge the photosensitive layer by corona discharge for 5 seconds, leave it for 5 seconds (the potential at this time is the initial potential Vo), and then charge the photosensitive layer. Light from a tungsten lamp was irradiated with the illumination intensity on the surface of 14 lux, and this operation was repeated for 100 lux.
Repeatedly. Measure the residual potential VX after 100 times, and
Ozone resistance was evaluated by VoX 100 (%). Also, the exposure i, E! required to reduce the initial potential from ±600V to ±IQOV! (lux seconds) was also measured. (2) A larger value of VoX100 (%) indicates less ozone deterioration, and a smaller f[(lux/sec) value indicates a highly sensitive photoreceptor. The results are shown in the attached table. As is clear from the attached table, by adding the compound of the present invention, the potential drop due to corona charging in the presence of ozone is significantly improved. Furthermore, it can be seen that there is almost no decrease in sensitivity due to the addition of the compound of the present invention.

[Brief explanation of the drawing]

1 to fjS4 are cross-sectional views of the photoreceptor of the present invention.

Claims (1)

[Scope of Claims] An electrophotographic photoreceptor in which a photosensitive layer containing a charge generating substance and a charge transporting substance as main components is provided on a conductive support, in which the photosensitive layer is represented by the following general formula [I]. An electrophotographic photoreceptor characterized by containing a spirobichroman compound. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. , represents a halogen atom, an alkyl group, an alkenyl group or an alkoxy group. R is an alkyl group, alkenyl group, cycloalkyl group, aryl group, heterocyclic group, R_4CO- group, R
_5SO_2- group or R_6NHCO- group, R
' is a hydrogen atom, an alkyl group, an alkenyl group, R_4CO
- group, R_5SO_2- group or R_6NHCO- group, R_4, R_5 and R_6 are each an alkyl group,
Represents an alkenyl group, cycloalkyl group, aryl group or heterocyclic group. R' is R_4CO- group, R_5SO_2
- group or R_6NHCO- group, R and R' may be the same group or different groups. ]